A Diastereoselective Intramolecular Hydroamination Approach to the Syntheses of (+)-, (±)-, and (−)-Pinidinol
- 16 May 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 66 (12) , 4344-4347
- https://doi.org/10.1021/jo015603n
Abstract
A diastereoselective, lanthanocene-catalyzed, intramolecular hydroamination reaction was applied to the preparation of 2,6-disubstituted piperidines. Various metal/ligand arrays in the catalysts were examined using a model substrate to allow optimization of the diastereoselectivity. It was determined that the relationship between metal size and ligand bulk plays an integral role in the transformation. The complex Cp*2NdCH(TMS)2 converted 2-substituted 8-nonen-4-amines to 2,6-disubsituted piperidines with greater than 100:1 selectivity for the formation of the cis isomer. A short synthesis of pinidinol, an alkaloid isolated from various pine and spruce species, was then carried out to exploit this stereoselective reaction.Keywords
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